CN107722127B - Process for producing cellulose ester - Google Patents
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- CN107722127B CN107722127B CN201710887648.9A CN201710887648A CN107722127B CN 107722127 B CN107722127 B CN 107722127B CN 201710887648 A CN201710887648 A CN 201710887648A CN 107722127 B CN107722127 B CN 107722127B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/02—Catalysts used for the esterification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/08—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate
- C08B3/10—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate with five or more carbon-atoms, e.g. valerate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
Abstract
The invention discloses a preparation method of cellulose ester. The invention is based on the reaction of cellulose with CO in the presence of an organic base2Reaction to form cellulose-based CO2Reversible ionic liquid compounds to effect CO thereof2One of the applications after dissolution and activation of reversible derivatization. The organic alkali is used as an effective component for dissolving cellulose and an organic functional catalyst for subsequent transesterification of the vinyl ester raw material and the cellulose, and can be repeatedly used, so that the preparation method is simple, and the production cost is reduced.
Description
Technical Field
The invention relates to the technical field of chemistry, in particular to a preparation method of cellulose ester.
Background
Cellulose is a biomass resource with the largest content on earth, and has the advantages of regeneration, biocompatibility, biodegradability, non-toxicity and the like, so the cellulose is considered as an important resource to replace petroleum-based resources to obtain products such as biodiesel, bio-based chemicals, bio-based materials and the like, and the full utilization of the cellulose resource has important significance for the sustainable development of the whole human society (Cao X, Sun S, Peng X, et al. journal of agricultural and food chemistry,2013,61(10):2489 and 2495).
Cellulose esters are an important one of cellulose derivatives, and some of the cellulose esters synthesized at present have been widely used in the fields of films, fibers, plastics, cigarette filters, and coating industries. Most cellulose esters are synthesized by esterification of cellulose with the corresponding acid, anhydride, acid chloride, etc. in either homogeneous or heterogeneous systems. However, the wide application of esterification reaction is limited by factors such as long time and harsh reaction conditions, while transesterification is an efficient method for synthesizing cellulose ester, and vinyl ester is the most common reactant for synthesizing cellulose ester in the transesterification reaction of cellulose (Cao X, Peng X, Zhong L, et al. cellulose,2014,21(1): 581-594).
However, cellulose itself is insoluble in general solvents due to its high molecular weight, high crystallinity, rigid backbone structure, etc., thereby limiting its corresponding chemical modification. With the discovery of new cellulose solvents, more and more dissolving systems can activate the dissolution of cellulose, and further carry out related chemical modification, particularly the chemical modification effect of cellulose in imidazole ionic liquids is particularly prominent (Vitz J, Erdmenger T, Haensch C, et al.Green chemistry,2009,11(3): 417-. However, ionic imidazoles ionic liquids are expensive and costly to recover, purify, and recycle, greatly limiting the economic performance of the process. In addition, there have been reports on the production of cellulose esters by transesterification of cellulose with vinyl esters using vinyl esters as a starting material, but there are major problems in that:
(1) longer reaction times are required (T.Heinze, R.Dicke, A.Koschella, A.H.Kull, E.A.Klohr and W.Koch, Macromolecular Chemistry and Physics,2000,201,627 631);
(2) higher temperatures (X.Cao, S.Sun, X.Peng, L.Zhong, R.Sun and D.Jiang, J Agric Food Chem,2013,61, 2489-2495);
(3) additional catalyst addition was required (J.Xie and Y.L.Hsieh, Journal of Polymer Science Part A Polymer Chemistry,2001,39, 1931-;
(4) or the use of more expensive dissolution systems (L.P.Hinner, J.L.Wissner, A.Berer, B.A.Nebel and B.Hauer, Green Chemistry,2016,18, 6099-.
The key technical obstacle of homogeneous modification of cellulose is to efficiently and mildly dissolve cellulose so as to activate hydroxyl on glucose repeating units. Chinese patent 201210374955.4 discloses a method for preparing a catalyst based on CO2Cellulose dissolving method of switch type solvent, its main characteristic is using cheap, easily prepared CO2Switching ionic compound or CO2The mixed solvent system consisting of the switching ionic compound and the organic solvent realizes the non-derivatization dissolution and CO of the cellulose2And (4) derivatization and dissolution. As a new cellulose dissolving system, a good platform is provided for homogeneous chemical modification of cellulose.
Disclosure of Invention
The purpose of the invention is: the preparation method of the cellulose ester is provided, wherein the organic base is used as an effective component for dissolving the cellulose and is also used as an organic functional catalyst for the subsequent transesterification reaction of the vinyl ester raw material and the cellulose, and the method is simple and easy to implement and has low cost.
The invention is realized by the following steps: a process for preparing a cellulose ester comprising the steps of:
1) mixing cellulose, organic alkali and an organic solvent to obtain a mixed system;
2) introducing carbon dioxide into the mixed system, reacting for 0.1-24h at 30-100 ℃ to obtain cellulose-based CO2A reversible ionic liquid compound;
3) to cellulose based CO2Adding vinyl ester into the reversible ionic liquid compound, and reacting at 20-120 ℃ for 0.1-48 hours to obtain a reaction mixed solution;
4) adding water or C1-C4 lower fatty alcohol into the reaction mixture, and filtering the reaction mixture containing lower fatty alcohol to obtain filtered solid;
5) purifying the solid mixture obtained by filtering with water or C1-C4 lower aliphatic alcohol, and drying to obtain cellulose ester.
The cellulose is one or any combination of several of microcrystalline cellulose, alpha-cellulose, cotton, wood pulp, bamboo pulp or plant cellulose separated from agricultural and forestry lignocellulose waste, and has a chemical structure shown in a formula (I):
wherein 50 < x < 1000.
The organic base has the following structural characteristics:
wherein:
in the A series, R1Is alkyl with 1-6 carbon atoms, R2,R3,R4Is independently methyl or ethyl;
in the B series, n is 1 or 2; m is 1-6; r is independently hydrogen, methyl or ethyl; r1Is independent hydrogen or alkyl with 1-6 carbon atoms; r2,R3,R4,R5Is independently hydrogen, methyl or ethyl.
The chemical structural formula of the organic base is shown as a formula (II), (III), (IV), (V) or (VI);
wherein: n is 1 or 2; r1Is independent hydrogen or alkyl with 1-6 carbon atoms.
The organic solvent is one or any combination of two or more of dimethyl sulfoxide, N-methyl pyrrolidone, tetramethylurea, tetraethylurea, N-dimethyl imidazolidinone, N-dimethyl formamide, N-diethyl acetamide, pyrrolidone, 2-nitrogen cyclohexanone, epsilon-caprolactam, N-dimethyl propylene urea, sulfolane and m-pentadiene sulfone.
In the mixed system in the step 1), the mass concentration of cellulose is 2-30%; the mass concentration of the organic alkali is 0.5-50%.
The reaction in the step 2) is carried out under a closed condition, and carbon dioxide is filled into the mixed system to ensure that the pressure of the carbon dioxide in the closed system is 0.1-15 MPa; the reaction temperature is 50-150 ℃.
Cellulose-based CO formed by the reaction of step 2)2The cation of the reversible ionic liquid compound has the following structural characteristics:
wherein:
in the A series, R1Is alkyl with 1-6 carbon atoms, R2,R3,R4Is independently methyl or ethyl;
b series, n ═ 1 or 2; m is 1-6; r is independently hydrogen, methyl or ethyl; r1Is independent hydrogen or alkyl with 1-6 carbon atoms; r2,R3,R4,R5Is independently hydrogen, methyl or ethyl;
the polyanion structure formed by the reaction has the following structural characteristics:
wherein 50 < x < 1000.
Vinyl ester and cellulose-based CO added in step 3)2The molar ratio of glucose units in the reversible ionic liquid compound is 0.1:1-10: 1.
The volume ratio of the low-grade fatty alcohol to the reaction mixed liquid in the step 4) is 0.5:1-10: 1.
The specific scheme for purifying the solid mixture obtained by filtering in the step 5) is to use C1-C4And (3) washing the solid mixture for 1-5 times by using lower aliphatic alcohol as a washing solvent, wherein the theoretical mass ratio of the washing solvent to the final reaction product cellulose proton type ionic liquid is 1:1-100: 1.
In step 5), the water or C1-C3The volume ratio of the lower aliphatic alcohol to the reaction mixed liquid is 0.5:1-10: 1.
In step 5), the water or C1-C3The volume ratio of the lower aliphatic alcohol to the reaction mixed liquid is 0.5:1-10: 1. C1-C3The lower aliphatic alcohol is one or more of methanol, ethanol or isopropanol, and the volume ratio of the lower aliphatic alcohol to the reaction mixed liquid is 2:1-5: 1.
The vinyl ester is one of the following structures:
wherein R is1＝CnH2n+1,(18≥n≥0)；R2＝CnH2n-1,(18≥n≥3)；R3＝CnH2n-3，(18≥n≥4)；R4，R5，R6，R7，R8Is independent hydrogen, halogen or alkyl with 1-6 carbon atoms; n is1＝1-20。
The invention is based on the reaction of cellulose with CO in the presence of an organic base2Reaction to form cellulose-based CO2Reversible ionic liquid compounds to effect CO thereof2One of the applications after dissolution and activation of reversible derivatization. The organic alkali is used as an effective component for dissolving cellulose and an organic functional catalyst for subsequent transesterification of the vinyl ester raw material and the cellulose, and can be repeatedly used, so that the preparation method is simple, and the production cost is reduced.
Drawings
FIG. 1 is a flow chart of the present invention;
FIG. 2 shows samples of cellulose benzoate1H NMR spectrum;
FIG. 3 shows samples of cellulose benzoate13C NMR spectrum;
FIG. 4 is a sample of cellulose pivalate1H NMR spectrum;
FIG. 5 is a sample of cellulose pivalate13C NMR spectrum;
FIG. 6 shows samples of cellulose cinnamate1H NMR spectrum;
FIG. 7 shows samples of cellulose cinnamate13C NMR spectrum;
FIG. 8 shows a sample of cellulose laurate1H NMR spectrum;
FIG. 9 is a sample of cellulose laurate13C NMR spectrum;
FIG. 10 is an infrared spectrum of a sample of cellulose benzoate;
FIG. 11 is a DSC of cellulose benzoates of varying degrees of substitution;
FIG. 12 shows that the A4 paper is modified to obtain a hydrophobic material with a water contact angle of 151.3 deg.
Detailed Description
Example 1 of the invention: a process for preparing a cellulose ester comprising the steps of:
a process for preparing a cellulose ester comprising the steps of:
1) mixing cellulose, organic alkali and an organic solvent to obtain a mixed system;
2) introducing carbon dioxide into the mixed system, reacting for 0.1-24h at 30-100 ℃ to obtain cellulose-based CO2A reversible ionic liquid compound;
3) to cellulose based CO2Adding vinyl ester into the reversible ionic liquid compound, and reacting at 20-120 ℃ for 0.1-48 hours to obtain a reaction mixed solution;
4) adding water or C1-C4 lower fatty alcohol into the reaction mixture, and filtering the reaction mixture containing lower fatty alcohol to obtain filtered solid;
5) and purifying and drying the solid mixture obtained by filtering to obtain the cellulose ester.
The flow chart is shown in the attached figure 1.
According to the above steps, different kinds of cellulose (0.65g) and organic base 1, 8-diazabicyclo [5.4.0 ] were weighed]1.83g of undec-7-ene (DBU) and 10g of dimethyl sulfoxide (DMSO) (the molar ratio of DBU to glucose units in cellulose is 3:1) are added into a high-pressure reaction kettle together and screwed tightly, and 0.5MPa of CO is introduced2Stirring the mixture at 50 ℃ for 1 hour to obtain activated cellulose, adding an equimolar amount of vinyl acetate or vinyl benzoate into the activated cellulose at 60 ℃ for reaction for 4 hours, washing the activated cellulose with methanol for 3 times after the reaction is finished, purifying and drying the activated cellulose to obtain the corresponding cellulose ester, wherein the corresponding experimental results are shown in the following table:
this example fully illustrates the general scope of the present patent with respect to cellulose types.
Example 2 of the invention: process for producing cellulose ester
According to the procedure of example 1, 0.65g of α -cellulose and 1, 8-diazabicyclo [5.4.0 ] organic base were weighed]1.83g of undec-7-ene (DBU) and 10g of dimethyl sulfoxide (DMSO) (the molar ratio of DBU to glucose units in cellulose is 3:1) are added into a high-pressure reaction kettle together and screwed tightly, and 0.5MPa of CO is introduced2And stirring and reacting for 1 hour at 50 ℃ to obtain a clear and transparent cellulose solution, wherein the concentration of the cellulose solution is 5 percent (mass fraction). Adding 5g of the solution into a two-mouth bottle, adding 0.69g of vinyl benzoate under mechanical stirring at 40 ℃ for reaction for 4 hours, adding 50ml of methanol into the mixed solution after the reaction is finished, washing the mixed solution for 3 times by using 50ml of methanol, washing the mixed solution for 3 times by using pure water, and freeze-drying the mixed solution for 24 hours to obtain the cellulose benzoate.
The substitution degree of the cellulose benzoate sample is 2.50 by nuclear magnetic characterization calculation. The nuclear magnetic hydrogen spectrum is shown in figure 2. The calculation formula is as follows:
wherein, IBenzeneRepresents the integral of the proton peak on the benzene ring, IH,AGURepresents the integral of the proton peak on cellulose.
Example 4 of the invention: process for producing cellulose ester
The procedure of example 1 was followed to investigate the applicability of the present invention to vinyl esters of different structures and different organic bases and the effect of reaction temperature and reaction time on the degree of substitution of the cellulose ester.
According to the steps of example 1, 0.65g of alpha-cellulose, 10g of organic base and dimethyl sulfoxide (DMSO) (the molar ratio of the organic base to the glucose units in the cellulose is 3:1) are weighed, put into a high-pressure reaction kettle together and screwed, and 0.5MPa of CO is introduced2Stirring and reacting for 1 hour at 50 ℃ to obtain a clear and transparent cellulose solution, wherein the concentration of the cellulose solution is 5 percent (mass fraction)Number). Adding 5g of the solution into a two-mouth bottle, adding vinyl ester with 3 times of the molar weight of the cellulose under mechanical stirring for reaction for a certain time, adding 50ml of methanol into the mixed solution after the reaction is finished, washing the mixed solution for 3 times by using 50ml of methanol, washing the mixed solution for 3 times by using pure water, and freeze-drying the mixed solution for 24 hours to obtain the cellulose benzoate. The specific results are as follows:
note: (1) DBU is 1, 8-diazabicycloundecen-7-ene, TMG is tetramethylguanidine, DBN is 1, 5-diazabicyclo [4.3.0] -5-nonene; (2) in order to determine the structure of the cellulose ester, the chemical structures of samples 1, 4 and 6 were characterized by nuclear magnetic resonance method, wherein the nuclear magnetic resonance spectrum and the carbon spectrum of sample 1 are shown in fig. 4 and 5, the nuclear magnetic resonance spectrum and the carbon spectrum of sample 4 are shown in fig. 6 and 7, and the nuclear magnetic resonance spectrum and the carbon spectrum of sample 6 are shown in fig. 8 and 9.
Example 4 of the invention: process for producing cellulose ester
The influence of different reaction times, reaction temperatures and ratios of vinyl ester to cellulose glucose unit moles on the degree of substitution of cellulose benzoate was examined according to the procedure of example 1.
According to the procedure of example 1, 0.65g of α -cellulose and 1, 8-diazabicyclo [5.4.0 ] organic base were weighed]1.83g of undec-7-ene (DBU) and 10g of dimethyl sulfoxide (DMSO) (the molar ratio of DBU to glucose units in cellulose is 3:1) are added into a high-pressure reaction kettle together and screwed tightly, and 0.5MPa of CO is introduced2And stirring and reacting for 1 hour at 50 ℃ to obtain a clear and transparent cellulose solution, wherein the concentration of the cellulose solution is 5 percent (mass fraction). Adding 5g of the solution into a two-mouth bottle, adding different contents of vinyl benzoate under mechanical stirring at different temperatures for reacting for different times, after the reaction is finished, adding 50ml of methanol into the mixed solution, washing for 3 times by using 50ml of methanol, washing for 3 times by using pure water, and freeze-drying for 24 hours to obtain the cellulose benzoate. The specific results are as follows:
in order to characterize the thermal properties of the cellulose benzoate with different degrees of substitution, DSC tests were performed on samples with numbers 4, 5 and 6, and the DSC spectra of the unmodified cellulose and the numbers 4, 5 and 6 are shown in figure 11. 4. Samples 5 and 6 correspond to curves C, A and B, respectively, of the DSC plot.
Example 5 of the invention: preparation method and application of cellulose ester
The transesterification of other celluloses and vinyl palmitate was examined using A4 paper as the starting material according to the procedure of example 1.
2.97g of A4 paper and 1, 8-diazabicyclo [5.4.0 ] organic base were weighed out according to the procedure of example 1]Adding 8.37g of undec-7-ene (DBU) and 300g of dimethyl sulfoxide (DMSO) (the molar ratio of DBU to glucose units in cellulose is 3:1) into a high-pressure reaction kettle, screwing, introducing 0.5MPa of CO2Stirring and reacting at 50 ℃ for 0.5 hour to obtain activated A4 paper, adding 15.53g of ethylene palmitate to the activated A4 paper mixture, reacting at 60 ℃ for 5 hours, taking out the modified A4 paper after the reaction is finished, washing with 50ml of methanol for 3 times, then washing with pure water for 3 times, and freeze-drying for 24 hours to obtain hydrophobic A4 paper, wherein the water contact angle of the obtained modified A4 paper is 151.3 degrees, as shown in the attached figure 12:
example 6 of the invention: preparation method and application of cellulose ester
The transesterification of other celluloses and vinyl palmitate was examined using commercial filter paper as the starting material according to the procedure of example 1.
5.94g of filter paper and 1, 8-diazabicyclo [5.4.0 ] organic base were weighed according to the procedure of example 1]11.16g of undec-7-ene (DBU) and 150g of dimethyl sulfoxide (DMSO) (the molar ratio of DBU to glucose units in cellulose is 2:1) are added into a high-pressure reaction kettle together and screwed tightly, and 0.8MPa of CO is introduced2Stirring the mixture at 50 deg.C for 0.5 hr to obtain activated filter paper mixture solution, adding 24.89g of vinyl laurate into the activated filter paper mixture, reacting at 100 deg.C for 12 hr, and taking out the mixture after the reaction is finishedThe modified filter paper was washed 3 times with 50ml of methanol and 3 times with pure water, and freeze-dried for 24 hours to obtain a hydrophobic filter paper, and the water contact angle of the modified A4 paper was 145 °.
Example 7 of the invention: process for producing cellulose ester
Different kinds of cellulose (0.65g), organic base 1, 8-diazabicyclo [5.4.0 ] were weighed out according to the procedure of example 1]1.83g of undec-7-ene (DBU) and 10g of dimethyl sulfoxide (DMSO) (the molar ratio of DBU to glucose units in cellulose is 3:1) are added into a high-pressure reaction kettle together and screwed tightly, and 1.0MPa of CO is introduced2Stirring and reacting for 4 hours at 50 ℃ to obtain activated cellulose, adding an equimolar amount of vinyl acetate into the activated cellulose at 50 ℃ to react for 4 hours, washing with methanol for 3 times after the reaction is finished, purifying and drying to obtain the corresponding cellulose ester. Degree of Substitution (DS) ═ 2.3. After byproducts such as methanol and the like are removed by rotary evaporation of the eluent, reduced pressure distillation is carried out again to obtain regenerated DBU and DMSO, wherein the regeneration rate of DBU is 98 percent, and the regeneration rate of DMSO is 96 percent. The regenerated DBU was reused in the reaction with DMSO and the reaction was repeated with a product Degree of Substitution (DS) of 2.4. This example fully illustrates the recyclability of the solvent in the patent of this invention.
Claims (5)
1. A method for preparing a cellulose ester, characterized in that: the method comprises the following steps:
1) mixing cellulose, organic alkali and an organic solvent to obtain a mixed system;
2) introducing carbon dioxide into the mixed system, reacting for 0.1-24h at 30-100 ℃ to obtain cellulose-based CO2A reversible ionic liquid compound;
3) to cellulose based CO2Adding vinyl ester into the reversible ionic liquid compound, and reacting for 4 hours at 40 ℃ to obtain a reaction mixed solution; the vinyl ester is vinyl pivalate, vinyl caprylate or vinyl laurate; and the ratio of vinyl ester to cellulose is 3mol/AGU or 4 mol/AGU;
4) adding water or C1-C4 lower fatty alcohol into the reaction mixture, and filtering to obtain filtered solid;
5) washing the solid mixture obtained by filtering with water or C1-C4 lower aliphatic alcohol, purifying and drying to obtain cellulose ester;
the chemical structural formula of the organic base is shown as formulas (II), (III), (IV), (V) or (VI);
wherein: n is 1 or 2; r1Is independent hydrogen or alkyl with 1-6 carbon atoms.
2. The process for producing a cellulose ester according to claim 1, characterized in that: the cellulose is one or any combination of several of microcrystalline cellulose, alpha-cellulose, cotton, wood pulp, bamboo pulp or plant cellulose separated from agricultural and forestry lignocellulose waste, and has a chemical structure shown in a formula (I):
wherein 50 < x < 1000.
3. The process for producing a cellulose ester according to claim 1, characterized in that: the organic solvent is one or any combination of two or more of dimethyl sulfoxide, N-methyl pyrrolidone, tetramethylurea, tetraethylurea, N-dimethyl imidazolidinone, N-dimethyl formamide, N-diethyl acetamide, pyrrolidone, 2-nitrogen cyclohexanone, epsilon-caprolactam, N-dimethyl propylene urea, sulfolane and m-pentadiene sulfone.
4. The process for producing a cellulose ester according to claim 1, characterized in that: the reaction in the step 2) is carried out under a closed condition, and carbon dioxide is filled into the mixed system to ensure that the pressure of the carbon dioxide in the closed system is 0.1-15 MPa; the reaction temperature is 50-100 ℃.
5. The process for producing a cellulose ester according to claim 1, characterized in that:
the volume ratio of the low-grade fatty alcohol to the reaction mixed liquid in the step 4) is 0.5:1-10: 1;
in step 5), the water or C1-C4The volume ratio of the lower aliphatic alcohol to the reaction mixed liquid is 0.5:1-10: 1; c1-C4The lower aliphatic alcohol is one or more of methanol, ethanol or isopropanol.
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| CN109232775A (en) * | 2018-09-18 | 2019-01-18 | 贵州大学 | A method of preparing cyclodextrin carbonic ester |
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| CN115677863B (en) * | 2022-11-22 | 2023-10-10 | 中国科学院宁波材料技术与工程研究所 | Method for preparing cellulose ester by microwave heating method in homogeneous system and cellulose ester |
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